DE2045126A1 - Process for the production of polyesters - Google Patents

Description

DR. ALFRED SCHÖN -8 MÖNCHEN 22. WIDENMAYERSTRASSE49 / I

See / Gl

6749-GE ./ SSR 61

! Marriage to Goodyear Sire & Rubber Company, ikron _s Ohio / USA

Process for the production of polyesters

The invention relates to improved polyester fiber films, coatings, adhesives, and molded articles, wherein for Production of the polyester both transesterification and polycondensation reactions in the presence of certain metal trifluoroacetates be carried out as catalysts »

According to the invention, a single super catalyst is both for carrying out cinester- as well as polycondensation reactions used to form polyesters that contain very little insoluble catalyst components, The scope of the invention also includes the production of

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Terephthalate-containing polyester » void. Copolyester in the presence of an improved catalyst. The polyesters according to the invention which have been produced in the presence of an improved catalyst are clear and non-cloudy polymers. The invention also provides for the production of a cocatalytic catalyst preparation which can be used during a transesterification and / or polycondensation,

According to the invention, polyesters in the presence of a catalytic Mange of certain metal trifluorine devices produced.

The polyesters according to the invention are cold-drawing linear ones highly polymerized esters from aromatic dibasic acids, such as terephthalic acid, naphthalic acid,

COOH, where R is a methylene group or

an alkyl-ubatituierte.Methylene group or oxygen or a carbonyl group, or from a halogen ring-substituted terephthalic acid, and glycols, such as HO (CHg) _n OH, where η is an integer from 2 - 10, branched glycols, such as 2 ₉ 2-dimethyl-1,3-propanediol, or other glycols such as cyclohexanedimethanol or the like. The copolyesters according to the invention can consist of ethylene terephthalate / ethylene isophthalate copolyesters as described in US Pat. No. 2,965,613. It can also be ethylene / neopentyl terephthalate copolyesters, copolyesters made from ethylene terephthalate and aliphatic dicarboxylates, ethylene and 1,3-trimethylene terephthalate, ethylene and tetramethylene terephthalate, tetramethylene terephthalate and isophthalate, ethylene terephthalate and isophthalate, ethylene phthalate and cyclohexane phthalate etc »act.

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Low molecular weight polyalkylene terephthalates can be prepared by the method described in US Pat. No. 3,427,287. ! The Glykolester obtained from terephthalic acid in the presence of the inventive catalyst at about 250 - mm 280 ⁰ C under a pressure of 0.05 to 20 mm Hg "completely polycondensed, said under cleaving of glycol, which is removed from the Reaktionsmisehung, the high polymers is produced.

Optionally, high polymer polyalkyl terephthalates can be produced in such a way that terephthalic acid bodies, such as, for example, the ester-forming derivatives of terephthalic acid _9, are heated with at least one glycol. Suitable ester-forming derivatives are aliphatic or aromatic esters of terephthalic acid , for example G ^ - to σ, -alkyl esters. The preferred derivative consists of methyl terephthalate

In the last-outlined method, which can optionally be carried out, a transesterification reaction (or an ester interchange reaction) takes place first with formation of the glycol ester and / or a lower polymer with liberation of alcohol. Subsequently, when heated to about 250-280 ⁰ C under a pressure of 0.05 to 5 »0 mm Hg absolute, a polycondensation reaction, whereby under cleavage (and removal) of glycolic the high polymers is formed. Any reaction is preferably catalyzed. Zinc acetate and other known catalysts are used to accelerate the esterification reaction. Antimony oxide or other known catalysts are used to promote the subsequent polycondensation reaction.

The manufacture of ethylene terephthalate / ethylene isophthalate copolyesters takes place according to US Pat. No. 2,965,613, with

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the exception that the catalysts according to the invention are used will.

Other linear aromatic polyester resins which are suitable for the purposes of the invention include not only polyalkylene terephthalate and copolyesters of ethylene terephthalate and ethylene aophthalate, but also other polymers, including those from CycloliexaMirae thyol terephthalate Polyethylene-2 _g 6-naphthalate, poly (alkylene} -terephthalate "in which the alkylene group contains 3-10 carbon atoms" as well as copolyesters from terephthalic acid, which contain at least 50 mol ~ $ terephthalic acid.

In the practice of the present invention, metal trifluoroethates can be used as the sole catalysts for making polyesters. For example, v / Ird aur production of 'Jerephthalat-containing polyester "and Oopolyestern which are obtained by transesterification of a C Cp his, -Dialkylterephthalats and Grlykol _f a polycondensation followed anschließet ;, as" Metalltrifluoracetat in an amount of 0 _f 0001-0 _f 05 Weight and as a precaution in an amount of 0.001 "" - 0 _? 02 6a · ™ weight (of the metal in the trifluoroacetate), "based on the weight of the diethyl terephthalate used.

Typical 'urifluoraoetate ^ which for the purposes erfindimgsgemäasen suitable _f include dio trifluoroacetate © the metals Mg, Ser .: Idf Ka _{f s} Ca Ba, Sr, Cd, Pb * Sb, Nb, Co, W, Ge, Zn " V _f T.if Sn etc The preferred metal trifluoraceous acts are the ™, jenigeii of magnesium and manganese.

3Ue amount of metal trifluoroacetate (based on the metal) is about 0 _? 0001 and Ο ,, Ο ^ Gev / ichts- ^ uxid voi'sugeweioe between 0 "001 and 0 _f O2 weight- ^ ,, related to the Dimethyl- · terephthalates ter.

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Will the polycondensation in the presence of SbgO ^ and * act as a catalyst _? carried out at least one Metalltrifluoraeetats »■ then, the amount of Antimonoxyds (based on the dimethyl terephthalate) _O9 about 001 - O _1, 5 wt ^ and preferably 0.005 - 0 ₈ 1 wt ^. In general, the cocatalytic preparation contains a major amount of SbgO ^ and a smaller amount of the metal trifluoroacetate. *

The following examples illustrate the invention.

Example \

2 »9 g of Mg (OH5 ₂ ~ powder are dissolved in 80 ml of distilled water, whereupon the solution is poured into a flask containing 10 ml of trifluoroacetic acid. The addition is carried out with vigorous stirring colorless. Subsequently, the contents of the flask is heated on a hot plate and stirred with a magnetic stirrer. Kaeh distilling-off of the whole water, and excess acid is this mixture very viscous the viscous material is. in a 10O ⁰ C oven for a period of 3 hours heated, a hard wise solid which is hygroscopic is obtained »The percentage of magnesium is _s as an X-ray fluorine analysis shows, 8.4 + 0.3 ^c ß> (theory; 9» 71 #) · ■ ■

0.2 mol of dimethyl terephthalate, 0.42 mol of ethylene glycol and 0 _s 0076 % magnesium metal (based on the dimethyl terephthalate) of magnesium trifluoroacetate are reacted in a glass tube reactor at 245 ° C for a period of 40 minutes under nitrogen and with stirring to achieve the To bring about transesterification reaction (Äah. The ester interchange reaction). The pressure is then gradually reduced to 1 mm Hg, absolute. the

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Polykondensatiorisreakfciox) is durchgsführi at 280 ⁰ G for a period of 1.5 hours ;. A very clear polyester with an intrinsic viscosity of 0 * 622, a carboxyl number of 60 (equivalents per 10 ^J g) UBd and a differential thermal analysis melting point of 255 ⁹ O is obtained. The term intrinsic viscosity is defined in US Pat. No. 2,965.

Example 2

The procedure described in Example T is durotage-filled, with the exception that a phosphorus stabilizer (0.04 $> riphenyl) phosphite, based on the weight of the dimethyl tetraphthalene tester) is used. The resultant non-turbid Ithylenterephthalat polymers besitat an intrinsic viscosity of 0.567, a carboxyl number of 16, a melting point of 26O ⁰ C (differential thermal analysis) and a G-ardner color of% 79.5 CCa) a -04 (b) "8 , 2).

The procedure described in Example 1 is repeated again, but in the presence of 0.025 ° f antimony trioxide as a cocatalyst sox ^ jS 0.03 fie pentaerythritol, based on the weight of dimethyl ^. A 15 minute long polycondensation at 280 ° 0, and at a pressure of 0.05 mm Hg absolute, is the Intrinaicviskosität 0,724e The polymer is not turbid and weitst a Carbo ^ lzahl 24 to "The melting point is 255 to ⁰ G (Differential thermal analysis) determined

Example ^

Following the procedure described in Example 2 is a Comparative experiment carried out, with the exception that a

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Manganese antimony: egg - Eatalyeatorsy8tem (manganese (llj-octoat - 0.0076 $ Manganese and antimony tri oxy el - 0 _s 031 $>? Based on the dimethyl terephthalate) is used. The older comparison polymer has an intrinsic viscosity of 0.600 * melting point of 256 ° C (differential thermal analysis) ,, a carboxyl (*. ■ 6.0 (a) "-0 _s 9 (!>).). These polymers is number 4 and a Gardner color of R _fl 72 6 somewhat cloudy. ■

2 g of manganese (III-caafboHat (reagent grade, manufactured by J ₀ T. Baker Chemical Co.) are slowly added to a beaker containing 5 g of urifluorescent acid. The addition is carried out with stirring. The reaction is gently heated while a gas (CO ₂ ) is set free «, The solution takes on a pale pink color.

The mixture is then heated in a beaker on a heis- Ben plate and stirred with a magnetic stirrer. The solution will turn dark in color when concentrated. The solution is filtered and the filtrate is concentrated to give a powdery pink colored solid.

This solid is then maintained at 65 ^{Θ Ο} dried under full vacuum, for a period of 16 hours and at a Exsikfcator "The percentage of bivalent manganese metal is 17» i 3 '~ _t such method is determined based on a RöntgenstrahlenflUQreszenz.

0.20 mol of dimethyl terephthalate, 0.42 mol of ethylene glycol and 0.0076 i> Manganmotall (based on the Dirnethylterephthalates ter) of Mangantrifluoracetat be in a Glasrohrreaktoi "by the method described in Example 1 Method for the implementation of

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brought. The intrinsic viscosity of the ethylene terephthalate polymer (the polymerization time is 2.5 hours) is found to be 0.413. The carboxyl number ″ is 28 and the melting point is 255 ⁰ O (differential thermal analysis). The polyester is essentially free from haze, as is determined by means of a visual examination.

Example 6

If example 5 is repeated with the exception that 0.025 # antimony oxide is used as cocatalyst, then the intrinsic viscosity of the ethylene terephthalate polymer is after a polymerization (i.e. polycondensation) of only 50 minutes 0.788, while the carboxyl number is 38 and the melting point (differential thermal analysis) determined to be 253 ° C will. The polyester is very clear from a visual inspection.

Example 7

A 11.3 kg (25 pound) -Charge an Ithylenterephthalat-polyester is prepared according to the method described in Example 6 are used except that in addition 0,04 i> of the triphenyl phosphite-Stabilisierungsroittels. The intrinsic viscosity of the polymer obtained is 0.757. The clear polyester obtained also has a carboxyl number of 12 and a melting point (differential thermal analysis) of 252 ° C. The thermal decomposition (broken bonds) is determined to be 0.04 and the hydrolytic decomposition to be 0.08 «

The thermal decomposition (expressed as fi broken bonds) is calculated according to the following equation:

$> Broken ties « IV waste χ k

Initial I.V. χ Bnd-I.V.

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IV Ast the xntrinslcviskoskositygwätüwl k © ine Sersetsungs ™ is constant. The investigation is carried out in such a manner that a dried sample is heated the polyester under dry and oxygen-free nitrogen over a period of 120 minutes at a precisely maintained temperature of 28O ⁰ O.

The hydrolytic decomposition, which is indicated as -Also $ broken bonds "-this is by heating" polyester sample determined in distilled water for a period of 16 hours at -i20 ^e C in a Wasserdampfaxitoklaven "JSs MiTSpL- the drop of the Intrinsioviskositäfc who carefully determined the prob ©, "

The dryness of the polyethylene tereishthalate polymers is shown in Table I. The turbidity is measured using an ^f i ^! measured by the caliper. This consists of an Idohtquelle (microscope illumination source), a heated aluminum block and a detector (milliammeter and photo inches). The reduction in the light intensity of a light beam through the sample is a measure of the turbidity of the sample. The higher the number, the more cloudy the polymer * The. The following values show the superiority of the Mn (OOOC3? ₅ ) ₂ catalyst over manganese ( It) acetate and Octasol catalysts.

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- to -

Table I.

Polymers ~ Mr. It ta out tans oh-. 5!: Eü.bungs ~ Hr _e

catalyst

1 Mn (GGCGJi ^) ₂ 58

2 Mti (0OCOFj) ₂ ^ ¹ ^ 63

3 'Mn CGOCGH ₅ ) ₂ 77

4 Mn Octasol ⁽²⁾ 217

5 Μα Octasol ^KJi J33

(1) Eg triphenyl phosphite is added as a stabilizing agent (0.04 #).

(2) Manganoctasol is manganese (II) oetoate in a hydrocarbon solvent that is phosphorus-free.

(3) Contains a phosphorus stabilizer ^

Example 8

0.38 mol of dimethyl terephthalate, 0.02 mol of dimethyl isophthalate ^ 0.42 mol of ethylene glycol and 0.0076 ψ of magnesium metal (based on the dimethyl terephthalate) of magnesium trifluoro acetate are in a glass tube reactor at 245 * 0 for a period of 45 minutes under oxygen-free and dry nitrogen and reacted with stirring, the glycol esters being formed by a heating reaction. The polycondensation reaction is carried out at 280 ^° C. for a period of 1.5 hours. A clear polyethylene terephthalate-isophthalate-copolyester polymer with an intrinsic viscosity of 0.630, a carboxy number of 50 and a differential thermal analysis melting point of 229 ° C. is obtained.

Example 9

0.195 moles of dimethyl terephthalate, 0.005 moles of Empol 1010 dimers

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Acid / ethylene glycol ester (Emery Industries * Cincinnati, Ohio), O ; 42 mol Äthyleiiglykcl and. Magnesium metal (based on the total ester weight) of magnesium trifluoro acetate are reacted according to the method described in Example 0, an ethyl ether terephthalate / dimerate copolyester being obtained which is very clear. The intrinsic viscosity is 0.615 and the differential thermal analysis melting point is 251 ° 0.

The above examples show that very clear polyethylene terephthalate polymers are obtained with molecular weights which are suitable for the production of films, fibers, coatings, etc. when a metal trifluoroacetate is used as the only catalyst for carrying out the ester exchange and polycondensation reaction. Mixtures of metal trifluoroacetate can also be used, for example Mg (OOCOE ₃ ) ₂ and Mn (OOCCT-Jg. In addition, the use of a customary polycondensation catalyst, such as SbgOj, GeO ₂ ^ a sitane compound, etc., is possible.

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Claims (1)

- 12 claims 1. A process for the production of polyesters by ester exchange and condensation reaction, characterized in that that both the ester interchange reaction and the condensation reaction in the presence of a catalytic amount at least a metal trifluoroacetate is carried out. 2. The method according to claim 1, characterized in that the metal trifluoroacetate used from a trifluoroacetate a Group II metal, a trifluoroacetate, a Group VII metal or a mixture thereof ". 5. The method according to claim 1, characterized in that the metal trifluoroacetate used is made from magnesium trifluoroacetate consists. 4. The method according to claim 1, characterized in that the metal trifluoroacetate used is made from manganese trifluoroacetate "consists. 5. The method according to claims 1-4, characterized in that the polyester used consists of polyethylene terephthalate "» 6. The method according to any one of claims 1-4, characterized in that that the polyester used is a copolyester. 7. polyester, characterized in that it according to the method has been produced according to any one of claims 1-6. 109817/2035